Acid amide derivatives of azo-dyestuffs



United States Patent The present application is aeontinuation-in-part of our co-pending application Ser. No. 273,364, filed February '25., 1952. The present invention relates to new acid amide derivatives of azo-dyes'tuffs which are free from sulfon'ic acid groups and :correspond to the general formula wherein R1 and R2 each represent a benzene radical, x stands -for hydrogen or an alkyl group of .low molecular weight and V is the radical of a non-vattable-diamine.

These acid-amidesare advantageously prepared by condensing2 molecular proportions of -a halide of the formula "(3) H1!) (EC-halogen or "one molecular proportion each of two different halides,

"both corresponding'to the Formula 3, with onemolecular proportion of a diamine ofthe formula (4) HR:QN-'H The meanings of R1, R2,=-R3 andx in Formulae 3 and 4 are shown in the-first paragraph.

The acid halides may be obtained by treating thezap- 'propriate carboxylic acids with acid halogenating agents.

These carboxylic acids of-the formula (5) H? 'coon may in turn be'preparedby methods in't'hemselves. known by coupling diazotized aminobenzoyl-aminobenzenes free from sulfonic acid groups with 2-hydroxy-naphthalene-3- carboxylic acid. There come more especially .into consideration l-amino-4-benzoylamino-benzenes, such as for example, 1-amino-4-benzoylaminobenzene without -further substituents, but the benzene nuclei may contain advantageously further substituents, such as for-instance .a halogen atom, preferably chlorine, alkyl-or alkoxygroups of .low molecular weight. benzenes of the formula Thus the aminobenzoyl-amino- 2,741,659 {Patented Apr. 10, .1955

wherein Y represents a chlorine atom-Oran alkoxy group of low molecular weight and Z stands for an alkyl- -or alkoxygroup of low molecular Weight, are, for instance,

vparticularly interesting. Asexamples of such diazo-components there may be-mentioned:

1 amine-2 5-dimethoxy-4-benzoyl=aminobenzene l-amino-2 5 -diethoxy-4-b enzoyl-aminobenzene 1-amino-2-methoxy-4 benzoylamino-5-methylb'enzene l-amino-Zwhloro-4-benzoylamino-5-methoxybenzene The azo-compounds containing carboxylic acid groups of Formula 5 are treated with agents capable of forming acid halides. As such agents there 'are to be understood those which are capable of converting carboxylic acids into their acid halides, for example their bromides or chlorides: there are especially suitable as such agents phosphorus halides, phosphorus pentabromide, phosphorus trich'loride, phosphorus pentachloride, or phosphorus oxyhalidesf It is of advantage to choose acid-.chlorinating agents, i. e. those which serve for the preparation of. the appropriate acid chlorides such as phosphorus pentachloride and thionyl chloride. 7 V V The treatment with such acid-halogenating agents is advantageously carried out in an inert organic solvent,

such as dimethyl-formamide, a chlorobenzene, for example, monoor dic'hloro-benzene, toluene, xylene, benzene or nitrobenzene.

In preparing such acid halides it is generally of ad- 'vantage first to dry the azo-compound produced in an aqueous medium or to free it from water 'by azeotropic distillation in an organic solvent. This .azeotropic dryinjg may, i fadesired, immediately precede the treatment with the 'halogenating agent.

As diamines of Formula 4 there are advantageously used those whose amino groups are both bound to aromatic carbon atoms, for example those in which Rs represents an aromatic radical, for instance a radical of the naphthalene or benzene series, in which the amino groups may be primary or, if desired, secondary. The diamines may be mononuclear, such as 1:4-diaminobenzene, 1:4-

diamino-Zz'S-dialkoxy-benzenes or 1:4-diamino-benzenes,

having in the 2- and 5rposition various substitueuts such as nitro-, halogen atoms, alkoxy groups, alkyl groups.

As a rulepart'icular'ly valuable results are obtained when diandpolynuclear amines are used, asfor instance, when 4':4'- diamino-diphenyl and its derivatives are used, for example, 3:'3'-dichloro-3:3-dimethyl-, 3:3 dialk'oxy 4:4-

diatriino-diphenyl, 3 i5 i3 :'5'-tetrachloro-4 4- diaminodi- 'phenyl and '3 :5 3'z'5' tetramethyl-4:4-diamiuo-diphenyl. In many cases valuable dyestuffs are also obtained by using diam'ines of the benzene series in'which two identical or diileren'tfben'zene nuclei arelinked together by asuitable f br id'ge member, for example, by oxygen, or an'SO2 group, as in the case, for example, of 4:4'-diainino-di- 'phenyl-sulfone, 3:3-diamino-4:4'-dicliloro-diphenyl sulfone, 3:?dianiino4:4'-dimethoxy-diphenyl stilfone, or' :a CO group such as for example, 3:3' diamino-diphenyl ketone, 3.:3-diamino-4:4'-dichloro-diphenyl kefone, 3:3-diamino-4g4' dimethoxy-diphenyl sulfone, or a --CHa group such as for example, 3:.3 cliamino-diif desired, to recrystallize the acid chlorides.

tion of the 7 acid chloride.

phenyl methane, 3 :3'-diamino-4:4' dichloro diphenyl methane, 4:4'-diamino-3 3'-dichloro-diphenyl methane, 4 :4'-diamino-3 :5 :3 5 -tetrachloro-diphenyl methane, or

chrysene, 4:1l-diamino-fiuoranthene, 2:6- or 1:5-diaminonaphthalene, 2:6-diamino-benz'thiazoles such as 2-(4'- amino-phenyl)-6-amino-benzthiazole.

the like. In order to accelerate the reaction it is generally desirable to remove the hydrochloric acid obtained during condensation, for example by continuous distillation, boiling under reflux or by adding an acid-binding agent such as anhydroussodium acetate, pyridine or anhydrous ammonia. The dyestufi's so obtained are in part crystalline and in part amorphous, and are generally obtained in very good yield and in a pure state. It may be of advantage, in

the acid chlorides obtained from the carboxylic acids, and In some cases, however, the isolation of the acid chlorides may be dispensed with without any harmful effects, and in some cases even with an improvement in the result, and the condensation carried out immediately following the prepara- If asymmetrical acid amide derivatives are to be prepared, the condensation of the diamine maybe carried out with the two different acid halides intwo stepsor in a single step.

The new acid amide derivatives of azo-dyestutfs accord- "ing' .to Formula 1 are pigments and as a rule are dis tinguished by an especially good fastness to migration and also by their temperature resistance and fastness to $01- vents. These properties are valuable above all 'for' socalledpigment printing, that is to say, printing processes which depend on fixing pigments by means of suitable adsions, or other emulsions (for example oil-in-water or' water-in-oil emulsions) or a substratum, especially on textile fibers but also on other fiat shaped structures such as paper (for example wall-papers) or fabrics made of glass fibers; The pigments can also be used for other pur- 7 order to produce especially pure dyestulfs, first to isolate poses, for example, in a finely dispersed form for dyeing I artificial silk made of viscose or cellulose ethers or esters or superpolyamides or super-polyurethanes in the spinning solution, also serve well in'the' manufacture of coloredlakes or lake formers, solutions and products made of acetyl cellulose, nitrocellulose, natural resins, or artificial resins such as polymerization or condensation resins, for example, aminoplasts, phenoplasts, polystyrene, polyethylene, polyacryl, rubber, casein, silicones and silicone resins.

'They can also be used with advantage in the manufacture of colored pencils, cosmetic preparations and laminated masses or preparationsof the aforesaid kind, and advantageously at a stage at which these masses or preparations have not yet reached their final shape. The operations necessary'for shaping, such as spinning, pressing, hardening, casting, sticking, can then be carried out without without any chemical reactions of the substratum such as 'and the acid chloride condensed with 9.2 dian'iinodiphenyl.

Example 1 49.9 parts of the azo-dyestutf from diazotized l-amino- 2:5-diethoxy 4 benzoyl aminobenzene and Z-hydroxynaphthalene-3-carboxylic acid are stirred in 300 parts of V ortho-dichlorobenzene. 15 parts of thionyl chloride are poured in and the whole heated to 120 to 130 C. for an hour while stirring. A warm solution of a temperature of C. of 9.2 parts of 4:4'-diamino-diphenyl in 50 parts of ortho-dichlorobenzene and 5 parts of anhydrous pyridine is added to the clear reddish blue solution and the whole is maintained at a temperature of 120-130 C. for 15 hours. It is then allowed to cool to C. and a current of dryammonia gas is introduced until a test portion gives a neutral reaction when stirred with water. The precipitated pigment isfiltered, thoroughly washed with warm ortho-dichlorobenzene at 100 C. mixed with hot Water while adding a dispersing agent and the dichlorobenzene adhering is distilled ofi with steam. The whole is then filtered and dried at 80 C. in vacuo.

There is obtained, a soft-grained, blue powder which dissolves in concentrated sulfuric acid with a greenish blue color and which colors polyvinyl chloride in pure reddish blue shades. Fastness to migration is very good.

By using 5.4 parts of 1:4-diaminobenzene instead of the 4:4'-diaminophe nyl there is obtaineda similar blue pigment. A reddish blue pigment is obtained when instead of 4:4'-diaminophenyl there isused 3:3-dichloro-4:4'-

diaminodiphenyl, and a greenish bluepigment is obtained when lz5-diamino-naphthalene is used.

Example 2 47.1 parts of the azo-dyestuff from diazotized l-amino- 2:5-dimethoxy-4-benzoylaminobenzene and Z-hydroxynaphthalene-3-carboxylic acid are converted into the acid chloride according to the method used in Example 1. The acid chloride is condensed with 4:4'-diaminodiphenyl also according to the manner described in Example 1.

A soft, reddish blue. powder is obtained which dissolves in concentrated sulfuric acid with a greenish blue colorand when incorporated by rolling inpolyvinyl chloridecolors it in reddish'blue shades of very good fastness I to migration. Stillpurer shades are obtained by using 3 3'-dichloro-4:4-diamino-diphenyl or 2:5-dichloro-1 :4- diaminobenzene instead of 4:4'-diamino-diphenyl.

Example 3 The pigment obtained'from 45.5 parts of the amdyestufi from diazotized 1-amino-2-methoxy-4-benzoylamino-S-methyl-benzene and 2-hydroxy-naphthalene-3- carboxylic acid :and 9.2 parts of 4:4f-diamino-diphenyl according to Example -1 is a soft violet powder, "which dissolves in concentrated sulfuric acid with a violet color and colors polyvinyl chloride in pure violet tints of very good fastness to migration. 7

By using 3:3'-dimethyl-4:4'diamino-diphenyl'or 3:3- dichloro-4:4'-diamino diphenyl instead of the 4:4- diamino-diphenyhthere is obtained a somewhat more reddish violet pigment having the same good fastness to migration.

Example 4 47.5 parts of the azo-dyestufi from diazotized l-amino- 2-chloro-4-benzoylamino-5-methoxy-benzene and 2-hy- 'droxy-naphthalene-3-carboxylic acidare converted into acid chloride according to the method used in Example 1,

parts of 4:4-

A -soft, violet powder is obtained which dissolves in concentrated sulfuric acid with a violet color and when 5 6 incorporated by rolling in polyvinyl chloride colors it in which R1 and R2 each represents an aromatic radical in violet tints of very good fastness to migration. of the benzene series, and R3 represents the radical of a By using 3:3'-dimethyl-4: V-diarnino-diphenyl or 3:3- non-vattable aromatic carbocyclic compound. dichloro-4:4-diamino-diphenyl instead of 4:4'-diamino- 2. An acid amide derivative of an azo dyestuff which diphenyl, similar tints are obtained. With 1:5-diamino- 5 derivative is free from sulfonic acid groups and correnaphthalene or 1:4-diaminobenzene dyestuffs are obsponds to the formula tained which color polyvinyl chloride in reddish blue in which Y represents a member selected from the group I tints consisting of a chlorine atom and an alkoxy group of low '1 What is claimed 15 molecular weight, Z represents a member selected from the group consisting of an alkyl group of low molecular 1. An acid amide derivative of an azo dyestuff, WhlCh Weight and an alkoxy group of low molecular weight derivative is free from sulfonic acid groups and correand R3 represents an aromatic radical containing only sponds to the formula carbocyclic rings and at the most two rings of this kind.

3. The acid amide derivative of the formula )0,H, no oo-HNONH-oo on moi-t 4. The acid amide derivative of the formula 0-013, nc oo-nNGONn-ot on moi-o 5. The acid amide derivative of the formula O-CH; m CID-ENO-ONH-OC on rho-t @CO.HN N=N M NW I OH;

6. The acid amide derivative of the formula m RH 01 H30- (ID-OH;

7. The acid amide derivative of the formula (B-CH:

No references cited. 

1. AN ACID AMIDE DERIVATIVE OF AN AZO DYESTUFF, WHICH DERIVATIVE IS FREE FROM SULFONIC ACID GROUPS AND CORRESPONDS TO THE FORMULA 